Tobacco composition on the like incorporating a polyiso-prenoid alcohol flavorsant

ABSTRACT

Tobacco products having improved flavor and smoking characteristics comprising tobacco and at least one polyisoprenoid hydrocarbon with optional polyisoprenoid esters and/or alcohols, the effective polyisoprenoid hydrocarbon may be represented by the formula.   Where n is an integer of from about 4 to 15 inclusive and the dotted line means that, at the position indicated, the bond can be either a single or a double bond, one double bond being present, and where x is an integer of 1 or 2 and y is an integer of 2 or 3, the value of x and y being determined by the position of the double bond.

ill States Patent [72] Inventor Ernst T. Theimer Rumson, NJ.

[2!] Appl. No 7.331

22 Filed Jan. 14, 1970 Division of Ser. No. 433J74, Feb. 16. 1965. Pat.No. 3.542.677

[45] Patented June 29, 1971 [73} Assignee international Flavors andFragrances Inc.

New York, NX.

[54] TOBACCO COMPOSITION ON THE LIKE INCORPORATLNG A POLYISO-PRENOIDALCOHOL FLAVORSANT 4 Claims, No Drawings [52] U.S.Cl 131/17,

[51] Int. Cl A24!) 15/04 [50] Field ofSearch 131/2, 17,

[56] References Cited UNITED STATES PATENTS 3,139,888 7/l964 Grossman eta]. 131/17 Primary Examiner-Melvin D. Rein Attorney-Ward, McElhannon,Brooks and Fitzpatrick Where n is an integer of from about 4 to 15inclusive and the dotted line means that, at the position. indicated,the bond can be either a single or a double bond, one double bond beingpresent, and where x is an integer of l or 2 and y is an integer of 2 or3, the value of x and y being determined by the position of the doublebond.

TOBACCO COMPOSITION ON THE LIKE INCORPORATING A POLYlSO-PRENOID ALCOHOLFLAVORSANT This application is a division of copending U.S. Pat.Application Ser. No. 433,174, filed Feb. l6, i965, now Pat. No.3,542,677.

This invention has to dowith a tobacco or tobaccolike product havingimproved smoking characteristics. More particularly, it relates toenhancing the flavor of tobacco containing products.

The term "tobacco" as used in this specification and the appended claimsmeans and includes, where the context permits, natural tobaccos such asburley, Turkish tobacco, Maryland tobacco, Virginia tobacco, andflue-cured tobacco; tobaccolike products such as reconstituted tobaccoor homogenized tobacco; and tobacco substitutes intended to replacenatural tobacco such as various vegetable leaves such as lettuce andcabbage leaves.

Recently there has been a marked trend in the tobacco industry towardthe use of filters in cigarettes, cigars and pipes. in addition,applications have been found for reconstituted or homogenized tobaccosand for synthetic wrappers and fillers as substitutes for naturaltobacco. Such smoking products have suffered from poor flavorcharacteristics. They are generally regarded as harsh, as containingundesirable aroma quality, and, they otherwise are considered as havingpoorer smoking flavor and less pleasant smoking character. Theseinnovations have magnified the need for improving the flavor of tobaccoproducts and otherwise enhancing the smoking characteristics of theseproducts. Of course, improved flavor may be obtained by the use ofhigher grade tobacco leaf. However, this is costly and there has beenincreased use of tobacco stems and poorer gradesof tobacco in variousblends.

It has been suggested that various additives or flavoring agents beincorporated with, or added to, tobacco products to improve theirflavor. For example, Grossman et al., U.S. Pat. No. 3,139,888, suggeststhe use of certain isoprenoid alcohols to impart a desirable flavor noteto tobacco. These additives and agents have not been uniformlysuccessful, and have suffered from a number of disadvantages. The maindisadvantages of the additives and agents previously proposed for thispurpose have been their relative unavailability, high cost, and inferioraroma and flavor. For example, the polyisoprenoid alcohol additivessuggested by Grossman et al., U.S. Pat. No. 3,139,888, have heretoforebeen obtainable by the extraction of naturally occurring plant sourcesor by noncommercial laboratory procedures. These processes areexpensive. Furthermore, these polyisoprenoid alcohols possess a floweryfragrance and impart undesirable aroma characteristics to tobaccoproducts.

Accordingly, it is an object of this invention to improve the flavor andsmoking characteristics of tobacco products.

In accordance with this invention it has been found that tobaccomaterials can be improved in flavor and smoking characteristics byincorporating in, or adding to, such materials a small but effectiveamount of a polyisoprenoid hydrocarbon or a mixture of a plurality ofsuch polyisoprenoid hydrocarbons. l have also found that tobacco andtobaccolike materials are enhanced in flavor when admixed with acomposition comprising certain polyisoprenoid hydrocarbons and certainpolyisoprenoid esters or polyisoprenoid alcohols or mixtures of saidesters and alcohols. Tobacco or tobaccolike products containing such apolyisoprenoid hydrocarbon, or mixtures of a polyisoprenoid hydrocarbonand a polyisoprenoid ester or a polyisoprenoid alcohol, are less harsh,more mild and have a strong tobacco taste and character and thisimproved taste, character and flavor is noted although the tobacco issmoked through a filter. Still another aspect of this invention is thepreparation of mixtures of the tobacco flavoring agents found useful inaccordance with this invention by refining, without degrading, as bymolecular distillation, crude mixtures of polyisoprenoid hydrocarbonsand polyisoprenoid esters formed as a residue after removing theconventionally distillable components of the reaction products obtainedby the controlled polymerization ofisoprene.

The polyisoprenoid hydrocarbons found effective as tobacco flavoringagents are represented by the formula where n'is an integer of fromabout 4 to 15 inclusive and the v dotted line means that, at theposition indicated, the bond can be either a single or a double bond,one double bond being present, and where x is an integer of l or 2 and yis an integer of 2 or 3, the value ofx and y being determined by theposition of the double bond. The data obtained from Nuclear MagneticResonance studies confirms the presence of vinylidene methylene groupsas well as of trisubstituted double bonds. Further, some or all of thehydrocarbons formed may contain a terminal menthadiene group of theformula in place of the terminal hydrogen shown in the above formula.Accordingly the formula given as representative of the polyisoprenoidhydrocarbons contemplates and includes all of the foregoing variations.Such polyisoprenoid hydrocarbons include: 2, 6, l0, l4-tetramethyl- 2,6, l0, l4-hexadecatetraene; 2, 6, l0, 14, I8, 22, ZtS-heptamethyl- 2, 6,l0, l4, 18, 22, 26cosaheptaene; 2, 6, l0, l4, i8, 22, 26, 30, 34-nona-methyl- 2, 6, l0, l4, i8, 22, 26, 30, 34-hexatriacontanonaene; 2,6, l0, l4, i8, 22, 26, 30 34, 38, 42, 46- dodecamethyl- 2, 6, l0, l4,18, 22, 26, 30, 34, 38, 42, 46-Octatetra-dodecaene, and the double bondisomers thereof. A plurality of such hydrocarbons may be used, andpreferably the molecularly distilled or purified mixture of hydrocarbonsobtained from the controlled polymerization of isoprene is employed asthe tobacco flavoring agent.

The polyisoprenoid hydrocarbons of this invention and mixtures of suchhydrocarbons with polyisoprenoid esters or polyisoprenoid alcohols havebeen found to possess a combination of properties which make themparticularly suitable as tobacco flavoring agents in that suchcompositions are effective at low concentrations and thus will not bleedinto tobacco wrapping materials, are low in cost, are stable onprolonged storage, resemble natural constituents of tobacco, are notknown to decompose on smoking to give materials which arephysiologically harmful, and their flavor enhancement is deliverablethrough a filter. The use of the polyisoprenoid hydrocarbons of thisinvention and mixtures thereof as tobacco flavoring agents also permitsgreater flexibility in experimenting with new blends of tobacco.

The polyisoprenoid hydrocarbons of this invention may also be admixedwith other polyisoprenoid materials such as polyisoprenoid esters oralcohols or mixtures of such polyisoprenoid esters and alcohols, andsuch mixtures of polyisoprenoidhydrocarbon and other polyisoprenoidmaterials have been found to be particularly convenient compositions tobe used as tobacco flavoring agents. The polyisoprenoid alcohols andesters found useful in this invention may be illustrated by the formulawherein n is an integer of from 4 to 15, inclusive, and R is an hydroxylradical or a lower aliphatic carboxylic acid eater radical such asformate, acetate, propionate and the like, and

the dotted line means that, at the positions indicated, the bond can beeither a single or a double bond, one double bond being present, andwhere x is an integer of l or 2 and y is an integer of 2 or 3, the valueofx and y being determined by the position of the double bond. The dataobtained from Nuclear Magnetic Resonance studies confirms the presenceof vinylidene methylene groups as well as of trisubstituted doublebonds. Further the esters or alcohols formed may contain a terminalmenthadiene group ofthe formula in place of the terminal hydrogen shownin the above formula. Accordingly, the formula given as representativeof the polyisoprenoid esters or alcohols contemplates and includes allof the foregoing variations. Such polyisoprenoid alcohols include: 2, 6,l0, l4-tetramethyl- 2, 6, l0, l4-hexadecatetraenel6- ol; 2, 6, l0, l4,I8, 22, 26-heptamethyl- 2,

. 6, 10, 14, 18, 22, 26-octacosaheptaene- 28 ol; 2, 6, l0, l4,

18, 22, 26, 30, 34-nonomethyl- 2, 6, l0, l4, i8, 22, 26, 30,34-hexatriacontanonaen- 36 2, 6, l0, l4, 18, 22, 26, 30, 34, 38, 42, 46-octatetracontadodecaen- 48 0|; and the double bond isomers thereof. Thepolyisoprenoid esters include the lower alkyl esters of the aforesaidalcohols. It should be understood that the useful polyisoprenoidalcohols represented by the above formula may include additional hydroxygroups in the chain or may have tertiary hydroxy groups rather thanterminal hydroxy groups and such materials would be consideredequivalent for purposes of this invention.

Although the mixture of polyisoprenoid hydrocarbon and otherpolyisoprenoid material may contain a broad range of amounts by weightof polyisoprenoid hydrocarbon to other polyisoprenoid material, it isconvenient that the polyisoprenoid hydrocarbon be present to a minoramount (less than 50 percent) by weight and the other polyisoprenoidmaterials in the mixture be present in a major amount (50 percent ormore) by weight since such compositions may be directly prepared by thecontrolled polymerization of isoprene in a lower aliphatic carboxylicacid. More particularly, the polyisoprenoid hydrocarbon may range fromabout to 40 percent by weight of the total polyisoprenoid mixture andthe 7 other polyisoprenoid material may range from about 85 to 60percent by weight of the total mixture.

The tobacco flavoring agent composition of this invention may beincorporated in, or added to, tobacco products by any of the usualtechniques including mechanical mixing, spraying, impregnation, coatingand other methods which will readily occur to those skilled in the art.The amount of the tobacco flavoring agent composition used will dependupon a number of factors including: the particular flavor or smokingcharacter desired, the particular tobaccos used, and the specific flavoragent composition employed. Generally the flavor agent mixture of thisinvention is admixed with tobacco or tobaccolike materials in amounts offrom about 0.25 to 6.0 percent by weight based on the weight of thetobacco materials. At proportions below about 0.25 percent littleimprovement is detected and at proportions much above about 6.0 percentnontobacco or objectionable flavors or aromas may be produced.

The tobacco enhancing compositions of this invention may also becombined with other flavor or aroma enhancing materials to obtain a moreesthetically pleasing combination of qualities. These can be formulatedas desired to obtain the particular nuances required. Other smokeenhancing ingredients with which the compositions of this invention maybe combined include: essential oils, balsam, fruit flavors such aspeach, walnut and cherry, coriander, coumarin, lactic acid andphenylacetic acid. Minty, spicy, nutty, fruity, and many other nuancescan be added to the compositions of this invention.

A mixture of polyisoprenoid hydrocarbons of suitable chain length may beprepared by the controlled polymerization of isoprene. In this respectionic polymerizations have been found to be more capable of beingcontrolled, and, therefore, are to be preferred in the practice of thisinvention. Further, a useful mixture of such polyisoprenoid hydrocarbonsand polyisoprenoid esters may be obtained directly by the COntrolledpolymerization of isoprene in a lower aliphatic carboxylic acid. Inthese processes the reaction mixture containing the desiredpolyisoprenoid materials of suitable chain length (C to C75) are refinedand separated from the nondistillable portions in such a manner that themixture is purified under low thermal hazard conditions so that thematerial is not decomposed or degraded. Molecular distillationprocedures have been found to be particularly effective in separatingthe desired polyisoprenoid materials from the undistillableobjectionable portions of the reaction product components withoutdegradation of the desired polyisoprenoid materials. For this purposethe spinning disc type of molecular still has been especially effectivesince it permits purification with the least thermal degradation,although, the wiping or brush-type" molecular still may be used. Ingeneral, the controlled polymerization is of the ionic type, and ispreferably carried out by reacting isoprene in a lower aliphaticcarboxylic acid and in the presence of a strong acid catalyst,preferably having a PH of 3 or less, under controlled temperatures andfor a period sufficient to obtain the desired chain length. Any loweraliphatic carboxylic acid may be used, although lower alkylmonocarboxylic acids such as acetic acid, propionic acid and the likeare preferred. The strong acid catalyst used may be a mineral acid suchas sulfuric acid and phosphoric acid, or acidic resins such assulfonated polystyrene resins like Amberlyst 15 made and sold by Rohm 8LHaas Company, and other strong acid equivalents.

The temperature and duration of the reaction will depend on a variety offactors including the economics of reaction time and conversionsdesired, and the specific organic acid and catalyst employed. Generally,the reaction temperature may vary from about 15 C. to 70 C. andtemperatures of form about 25 C. to 35 C. are preferred since at lowertemperatures the reaction time is slowed, while at temperatures muchabove 70 C. the reaction may proceed too quickly, higher polymers ofisoprene may be formed, and a closed system and super atmosphericpressure is required to prevent loss of the volatile isoprene. The timeof the reaction may vary from about 5 to 200 hours, and preferably thereaction period is from about 50 to hours.

When the reaction is completed, the acid catalyst is neutralized by theaddition of a basic material or removed from the reaction mixture, andthe unreacted materials and the reaction products of chain length belowabout C may be separated by any conventional method. Preferably, suchproducts are separated by distillation. The residue from this separationcontaining products of about C and higher chain lengths is furtherrefined by molecular distillation, and the distillate from thismolecular distillation contains a tobacco flavor agent compositioncomprising the polyisoprenoid hydrocarbons and polyisoprenoid esters ofthis invention and the composition obtained may be used as such withoutfurther treatment. Since the polyisoprenoid hydrocarbons are thepreferred flavoring agents the polyisoprenoid esters formed in thereaction may be converted, if desired, to the correspondingpolyisoprenoid hydrocarbons by pyrolysis or any of the conventionalprocesses.

in still another embodiment, the said composition of polyisoprenoidhydrocarbons and polyisoprenoid esters may be saponifled by reactionwith a strong alkali-material to yield a mixture of polyisoprenoidhydrocarbons and polyisoprenoid alcohols, which may also contain somepolyisoprenoid esters depending upon the degree of hydrolysis obtained.The saponified mixture after purification by molecular distillation isalso effective as a tobacco enhancing agent.

The following example will serve only to illustrate the invention morefully; and accordingly they are not to be construed as limiting thescope of the invention.

Example 1 To a flask fitted with reflux condenser, stirrer andthermometer 3,000 gm. of isoprene, 3,000 gm. of glacial acetic acid, 15gm. of water, 7 gm. of hydroquinone, and 10 gm. of concentrated sulfuricacid were charged. The mixture was stirred for 6 hours and then allowedto stand at about 25" C., for 120 hours, stirring for 30 minutes aftereach 24 hours period.

The catalyst was then neutralized by adding 50 gm. of anhydrous sodiumacetate to the mixture, and the mixture was stirred until the salt wasdissolved. The reflux condenser was replaced with a distillation headand the reaction mixture heated to 50 C. A fraction weighing 703 gms.was obtained. This fraction was essentially pure isoprene.

The pressure was reduced to 100 mm. Hg and the temperature of thereaction mixture held at 50 C. A fraction weighing 545 gms. wasobtained. This mixture consisted of 235 gms. (43 percent) of acetic acidand 310 gms. (57 percent) of isoprene.

The pressure was reduced to 3 mm. Hg and the temperature of the reactionmixture held at 50 C. A fraction weighing 2,462 gms. was obtained. Thisfraction consisted of 2,157 gms. (87.6 percent) of acetic acid and 305gms. (12.4 percent) of prenyl acetate.

The pressure was held at 3 mm. Hg and the temperature of the reactionmixture slowly raised to 200 C. The distilled fraction was condensed andcollected. lt weighed 942 gms.

The residue weighed 256 gms.

The distilled fraction was washed once with an equal volume of waterthen once with an equal volume of 3 percent sodium carbonate andsubjected to fractional distillation and the results obtained aresummarized in the following table:

Weight collected Yield Compound type (gms.) percent C5 compounds. 43314. 4 Cu) compounds.....-. 600 20. (315-20 compounds. 153 5. 1 Residue256 it 6 Example 2 The crude residue product of example 1 prior tomolecular distillation comprising a mixture of polyisoprenoidhydrocarbons and polyisoprenoid acetates was saponified as follows:

To kg, of the residue of example 1 was added 8 liters of 20 percentpotassium hydroxide in methanol. The reaction mass was then neutralizedwith hydrochloric acid, washed with water and extracted with petroleumeither. The ether extract was dried and flash evaporated leaving 4,176grams of a crude mixture. The crude mixture was then molecularlydistilled on a spinning disc molecular distillation unit and yielded acomposition composed of about 30 percent by weight of C to Cpolyisoprenoid hydrocarbons and 70 percent by weight of C to Cpolyisoprenoid alcohols.

Example 3 The saponified product of example 2 was further refined andseparated in the following manner:

The 4,176 grams of saponified product of example 2 was diluted with 6liters of n-hexane, and 20 pounds of activated silica gel was slowlyadded with stirring. The silica gel was filtered and washed with 10liters of hexane. The wash and filtrate were combined and flashevaporated, yielding 1,817 grams of hydrocarbon material.

1.4 kg. of this hydrocarbon fraction was distilled on a spinning discmolecular distillation unit. 11 fractions weighing 878 grams wereobtained. These fractions are listed as follows:

Boiling Refractive The silica gel was then washed with 12 liters ofmethanol. The wash liquid was flash evaporated leaving 1,396 grams ofcrude alcohols. This material was distilled on a spinning disc molecularstill. Twelve fractions weighing 916 grams were obtained.

Boiling Refractive Alcohol point, C. Pressure index Iodine tractionNumber (rotor temp.) (mm. Hg) (nD Number Example 4 To a flask fittedwith reflux condenser, stirrer and thermometer was added 3,000 gms. ofisoprene, 3,000 gmsnof propionic acid, 15 gms. of water, 7 mgs. ofhydroquinone and 10 gms. of concentrated sulfuric acid. The mixture wasstirred for 30 minutes at the end of each 24 hour period. The reactionwas then stopped by neutralizing the catalyst by adding and dissolving58 grams of anhydrous sodium propionate.

The reflux condenser was replaced with a distillation head and condenserand the reaction mixture heated to 50 C.

A fraction of pure isoprene weighing 702 grams was ob tained. Thepressure was reduced to 100 mm. Hg and the temperature of the reactionmixture maintained at 50 C. A fraction weighing 1,304 grams andconsisting of 29 grams (2.2 percent) propionic acid and 1,275 grams(97.8 percent) of isoprene was obtained.

The pressure was reduced to 3 mm. Hg and the temperature of the reactionmixture maintained at 50 C. A fraction weighing 2,982 grams andconsisting of 179 grams (6 percent) prenyl propionate and 2,803 grams(94 percent) of propionic acid was obtained.

The pressure was held at 3 mm. Hg and the temperature of the liquidslowly raised from 50 C. to 200 C. A fraction weighing 277 grams wascollected. As residue, 192 grams were obtained.

The distilled fraction was washed once with 600 mls. of water and thenonce with 600 mls. of 3 percent aqueous sodium carbonate, and subjectedto fractional distillation. The results obtained are summarizedthgtablebelgg The residue was distilled on a spinning disc moleculardistillation unit. The resulting product comprised a mixture of C to Cpolyisoprenoid hydrocarbons and a mixture of C to C polyisoprenoidpropionates. in which the ester proportion of the mixture representedabout 70 percent by weight.

The resulting product may then be saponified as in example 2 andseparated into hydrocarbon and alcohol fractions in accordance with theprocedure set forth in example 3.

Example A series of tobacco blends were prepared by spraying a solutionof each of the flavoring agents shown in the following tabulation onto atobacco blend consisting of 55 percent weight of Type 12 Virginiatobacco and 45 percent by weight of Burley tobacco. The solutioncomprised 1 percent of each of said flavoring agents based on the weightof the tobacco blend and equal parts by volume of hexaneand specialdena' tured number 4 ethyl alcohol. Each of the sprayed tobacco blendswas air dried, made into cigarettes and allowed to age over night. Thecigarettes were then smokedand evaluated by a panel of experts and theresults indicated in the tabulation were noted.

Flavoring agent employed Evaluation comment Strong tobacco flavor..\lilder agent 2 of this tabulation.

4. Hydrocarbon traction 1 of Example 3.

5. Hydrocarbon fraction 3 of Ex- Do.

ample 3.

6. Hydrocarbon fraction 5 of Ex- Do. ample3.

7. Hydrocarbon fraction 7 of Ex- Do.

ample3.

8. Hydrocarbon traction 9 of Ex- Do.

ample'o.

9. Hydrocarbon fraction ll of Ex- Do.

ample 3. 10. Alcoholtractlon lof Example 3. 11. Alcohol fraction 3 ofExample 3. 12. Alcohol fraction 5 of Example 3. 13. Compositlve of 12alcohol tractions of Example 3.

14. The molecularly distilled prodnet of Example 2 comprising a mixtureor (320-075 p01yisoprenoid hydrocarbons and C -C 5 polyisoprenoidalcohol. V

Strogg flowery-chemical ofl taste.

Some ofl taste. Hot suitable at concentrations greater than 1% byweight.

Less harsh and smoother than control but not as good as flavoring agentsNos. 2 and 3 of this tabulation.

Example 6 To a 3 neck flask fitted with reflux condenser, stirrer andthermometer was added 3,000 gms. of isoprene, 3,000 gms. of glacialacetic acid, 15 gms. of water, 7 gms. of hydroquinone and 41.6 gms. ofAmberlyst l5 sulfonated polystyrene ionexchange resin. The mixture wasstirred continuously for 126 hours.

50 gms. of anhydrous sodium acetate was then added to the mixture andstirred until dissolved. The reflux condenser was replaced with adistillation head and condenser and the reaction mixture heated to 50 C.A fraction pure isoprene weighing 592 gms. was obtained.

The pressure was reduced to 100 mm. Hg. and the temperature of thereaction mixture held at 50 C. A fraction weighing 672 gms. andconsisting of 325 gms. (48.4 percent) of acetic acid and 347 gms. (51.6percent) of isoprene was obtained. The reaction mixture was cooled andfiltered under slight vacuum to remove the ion-exchange resin. Thefiltrate was distilled at a pressure of 3 mm. Hg. maintaining thereaction mixture at 50 C. A fraction weighing 2,363 gms. and consist- Iing of 1,914 gms. (81 percent) of acetic acid and 449 gms. 19

percent) of prenylacetate was obtained. The pressure was held at 3 mm.and the temperature of the liquid slowly raised from 50 C. to 200 C. Afraction weighing 569 gms. was obtained. A residue of 55 gms. wasobtained.

flavor. Smoother than flavoring The residue of 55 gms. may then bedistilled on a spinning disc molecular still. The resulting distilledproduct comprises a mixture of C to C polyisoprenoid hydrocarbons and amixture of C and C polyisoprenoid acetates, in which the ester 5 portionof the mixture represents about 70 percent by weight.

The distilled mixture is blended with tobacco at l percent by weightconcentration and enhances the flavor of the blend when smoked.

Example 7 4 kg. of the residue obtained in example 1 was distilled on aspinning disc molecular distillation unit as described in example l,yielding 3.2 kg. of distilled product comprising a mixture of c te Cpolyisoprenoid hydrocarbons and a mixture of C to C polyisoprenoidacetates, in which the ester portion of the mixture represented about 70percent by weight.

This material was passed through a steel tube packed with porcelainsaddles at 400 C. In a nitrogen atmosphere, yielding 20 about 1,400 gms.of a product consisting substantially of polyisoprenoid hydrocarbonshaving the same chain length as the hydrocarbons of example 3. The crudepyrolysate mixture was washed with aqueous sodium bicarbonate solutionto remove the acetic acid formed in the pyrolysis, dried, and distilledon a spinning disc as in example 3. There were obtained 11 fractions ina temperature range of 85 C. to 185 C. (rotor temperature) atapproximately 0.03 to 0.02 mm. Hg. pressure. Of these fractions, thefirst three were discarded. The remainder of about 1,100 gms. wereevaluated and were found to have substantially the same smokingproperties as the product of example 3.

The invention in its broader aspects is not limited to the specificcompositions, combinations and improvements described, but departuresmay be made therefrom within the scope of the accompanying claims andtheir equivalents without departing from the principles of the inventionand without sacrificing its chief advantages.

What 1 claim is:

1. A tobacco product having improved flavor and smoking characteristicscomprising tobacco and from about 0.25 to 6.0 percent by weight based onthe weight of the tobacco of a polyisoprenoid hydrocarbon represented bythe formula of a mixture of (i) a polyisoprenoid hydrocarbon representedby the formula V W CHzC-CH,CH HI: 1 1 H CH, :1 where n is an integer offrom about 4 to 15 inclusive and wherein each dotted line is a bondselected from the group consisting of a single bond and a double bond, adouble bond being present, and wherein x is an integer of from 1 to 2and y is an integer of from 2 to 3, the value ofx and y being determinedby the position of said double bond, and (ii) a polyisoprenoid compoundrepresented by the formula 4. A smoking product as defined irv claim 2,wherein said polyisoprenoid compound is a polyisoprenoid lower aliphaticcarboxylic acid ester.

W050 7 UNITED STATES PATENT OFFICE a 5 9 CERTIFICATE OF CORRECTIONPatent No, 315891372 3 Dated June 29, 197].

Inventt(s) ERNST T. THEIMER It is certified that error appears in theabove-identified patent and that said Letters Patent are herebycorrected as shown below:

r- Iitle page, correct the title to read: .1

-TOBACCO COMPOSITION OR THE LIKE INCORPORA'IING A POLYISO-PRENOIDALCOHOL FLAVORANT- Title page, in the Abstract, Col. 2, line 7, C01. 8,line 45, (claim 1) and at Col. 8, line 57, (claim 2) the formula shouldread:

H-HC-H-H-H H n C Y Col. 2, line 68, and at Col. 8, line 67, (claim 2)the formula should read:

H -CH (I CH -CH R CH n Col. 2, line 35, "cosaheptaene" should read--octacosaheptaene- Col. 5, line 63, "either" should read -ether-.

Col. 7, line 43, "hot" should read --not- Col. 8, line 19, "400C. In a"should read --400C. in a-- L Signed and sealed this 21 st day of March1972. J

(SEAL) Attest: EDWARD M.FLETCHER,JR. ROBERT GOT'ISCHALK AttestingOfficer Commissionerof Patents

2. A tobacco product comprising tobacco and from about 0.25 to 6.0percent by weight based on the weight of tobacco of a mixture of (i) apolyisoprenoid hydrocarbon represented by the formula
 3. A tobaccoproduct as defined in claim 2, wherein said polyisoprenoid compound is apolyisoprenoid alcohol.
 4. A smoking product as defined in claim 2,wherein said polyisoprenoid compound is a polyisoprenoid lower aliphaticcarboxylic acid ester.